A method and system for producing 1,4-butanediol (1,4-BG), and optionally additionally tetrahydrofuran (THF), that promotes more efficient usage of water (H2O) is provided. In one aspect, the method is comprised of supplying at least one feed stream including 1,4-diacetoxybutane (1,4-DAB), 1,4-hydroxyacetoxybutane (1,4-HAB) and H2O to at least one reactor. 1,4-DAB, 1,4-HAB and H2O are reacted in the reactor to produce at least one effluent stream that includes 1,4-BG, 1,4-HAB, H2O, unreacted 1,4-DAB and acetic acid. The effluent stream is supplied to a separation system having one or more separators where at least a portion of the 1,4-HAB is removed from the effluent stream and recycled back to the reaction. Alternatively, 1,4-HAB may be supplied directly to the reactor as a feed stream, or a combination of feed stream and recycled 1,4-HAB may be used.
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9. A method of increasing the production of butanediol in a hydrolysis reaction system characterized in that reactants 1,4-diacetoxybutane (1,4-DAB), 1,4-hydroxyacetoxybutane (1,4-HAB) and water (H2O) are reacted in a reactor to produce an effluent stream comprising substantially 1,4-butanediol (1,4-BG) and 1,4-HAB wherein the following equations are satisfied:
where Max=(7.59D-0.76)/n Min=(3.79D-2.00)/n Var=B/A D=174(C)/90(A) and where A is the feed rate of 1,4-DAB to the reaction system in kg/hr; B is the feed rate of fresh 1,4-HAB to the reaction system plus the total amount of 1,4-HAB recycled to the reaction system in kg/hr; C is the amount of 1,4-BG produced by the reaction system, and n is the number of reactors within the reaction system.
1. A method of producing 1,4-butanediol (1,4-BG) in a hydrolysis reaction, comprising the steps of:
supplying at least 1,4-diacetoxybutane (1,4-DAB), 1,4-hydroxyacetoxybutane (1,4-HAB), and water (H2O) to at least one reactor; reacting said 1,4-DAB, 1,4-HAB and H2O to produce an effluent stream comprising 1,4-BG, 1,4-HAB, H2O and acetic acid; supplying said effluent stream to a separation system having at least one separator wherein said H2O and acetic acid are separated in a purge stream, and at least one product stream is produced comprising 1,4-HAB and 1,4-BG, wherein the following equations are satisfied: where Max=(7.59D-0.76)/n Min=(3.79D-2.00)/n Var=B/A D=174(C)/90(A) and where A is the feed rate of 1,4-DAB to the reaction system in kg/hr; B is the feed rate of fresh 1,4-HAB to the reaction system plus the total amount of 1,4-HAB recycled to the reaction system in kg/hr; C is the amount of 1,4-BG produced by the reaction system, and n is the number of reactors within the reaction system; and wherein the one or more product stream is substantially comprised of 1,4-BG.
2. The method of
3. The method of
4. The method of
Min'≦Var≦Max where Max=(7.59D-0.76)/n Min'=(3.79D-1.46)/n Var=B/A D=174(C)/90(A) and where A is the feed rate of 1,4-DAB to the reaction system in kg/hr; B is the feed rate of fresh 1,4-HAB to the reaction system plus the total amount of 1,4-HAB recycled to the reaction system in kg/hr; C is the amount of 1,4-BG produced by the reaction system, and n is the number of reactors within the reaction system.
6. The method of
7. The method of
8. The method of
10. The method of
Min'≦Var≦Max where Max=(7.59D-0.76)/n Min'=(3.79D-1.46)/n Var=B/A D=174(C)/90(A) and where A is the feed rate of 1,4-DAB to the reaction system in kg/hr; B is the feed rate of fresh 1,4-HAB to the reaction system plus the total amount of 1,4-HAB recycled to the reaction system in kg/hr; C is the amount of 1,4-BG produced by the reaction system, and n is the number of reactors within the reaction system.
11. The method of
13. The method of
14. The method of
15. The method of
16. The method of
17. The method of
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The present invention relates to a method and system for producing butanediol, and in particular 1,4-butanediol (1,4-BG). More specifically, the present invention relates to a method and system for producing 1,4-BG in a hydrolysis reaction wherein 1,4-hydroxyacetoxybutane (1,4-HAB) is utilized as a starting material or reactant which acts to shift the equilibrium of the hydrolysis reaction to reduce the amount of water (H2O) required to carry out the hydrolysis reaction. Moreover, it leads to an overall optimum total operating cost which includes utility and capital cost considerations.
Butanediols, and in particular 1,4-butanediol (1,4-BG), find wide use in the chemical industry. 1,4-BG is used for a variety of purposes, and notable examples of its utility include use as a raw material for the production of a number of chemicals such as for the production of polyester. A number of processes are conventionally utilized to produce 1,4-butanediol. Conventional methods generally employ a hydrolysis reaction to produce 1,4-butanediol. For example, butadiene is reacted in an acetoxylation reaction with acetic acid (AcOH) and Oxygen then further hydrogenated to form 1,4-diacetoxybutane (1,4-DAB). 1,4-DAB is then further reacted with water (H2O) in liquid phase to produce 1,4-BG, 1,4-hydroxyacetoxybutane (1,4-HAB) and AcOH. Therefore, the product stream generally includes 1,4-HAB, AcOH, unreacted 1,4-DAB and various by-products. Purified 1,4-BG is typically recovered by multiple distillation steps. Typically, the 1,4-HAB and unreacted 1,4-DAB may be further reacted with H2O at different reaction conditions to form tetrahydrofuran (THF).
These conventional methods of producing 1,4-BG and additionally THF, are very energy intensive. Very large amounts of H2O are consumed in the hydrolysis reaction. One conventional method of reducing the amount of H2O used in the reaction is to employ more than one reaction/separation stage. An example of one illustrative embodiment of a prior art reaction system 10 is shown in
To reduce the total amount of fresh H2O consumption, an alternative embodiment of the system 10 may be used; where typically, fresh H2O will only be added to the last stage of the reactors (i.e. 12c) in series, as shown in
To understand the relationship of H2O usage (and therefore energy consumption) to the amount of 1,4-BG and 1,4-HAB production, lets start with the simple case of a system having one reactor stage with no recycle stream or system.
To reduce this amount of total H2O usage and/or energy consumption, one method used is to introduce an additional number of reactors to the system 10, as mentioned above. Moreover, since the system is employing multiple reactor stages, it is possible to reduce the total amount of fresh H2O by recycling the H2O from the separators to one or more of the previous reactors. However, in doing so, there is a very small penalty on the total amount of H2O usage.
There is another element that needs to be considered when determining the best overall performance of the system 10. This additional element is the capital cost of the system 10. For this hydrolysis reaction system, since it is an equilibrium reaction and the reaction conditions are close to equilibrium. Further, the amount of H2O flow in the system is almost equal to the total flowrate at the system due to the small value of equilibrium constant. Therefore, the amount of total H2O usage can be used as the measurement of the capital cost. This is because as the system uses more H2O, the reactor size is greater, and consequently the capital cost of the system is higher.
While the amount of H2O usage, and thus the energy consumption or costs, associated with producing 1,4-BG and additionally THF are reduced by employing more reactor stages (i.e. reactors/separators) and H2O recycle streams, the capital costs increase with the addition of these units. The prior art system configuration employing three reactors/separators and two H2O/AcOH recycle streams is desirable from both an energy and capital cost point of view. For the capital cost, although this prior art configuration uses two additional reactors as compared to the single reactor case, the total flow rate for the reactor system is significantly smaller than that for the single reactor case. Consequently, the size of the equipment is much smaller and this offsets the cost of the additional equipment necessary for the three-reactor configuration. Hence, in this instance the total capital cost for the three reactors with two H2O/AcOH recycle streams is lower than that for the one reactor with no H2O/AcOH recycle. However, there are many variables, constraints and tradeoffs between the energy costs and capital costs that must be considered.
Another technique that has been employed in the prior art is to recycle 1,4-HAB produced in the reaction back to the reactor. For example, Japanese Patent No. 55-16489 discloses recycling AcOH, diols and/or 1,4-HAB to a reactor. Japanese Patent No. 11-169435 describes recycling an effluent stream including 1,4-HAB to one or more reactors and focuses on reducing the amount of 1,4-HAB recycle. While these methods have provided an improved process, further improvement is desirable. Moreover, in these prior art patents it is believed that the desirable product is only 1,4-BG. Consequently, 1,4-HAB is considered as a waste and thus recycling it will be desirable. Accordingly, it would be highly desirable to provide a method and system for producing 1,4-BG, and optionally additionally THF, which promotes the more efficient usage of H2O and is capable of minimizing both the operating or energy costs of production and the capital expense of the system.
Accordingly, in summary, it is an object of the present invention to provide a method and system for producing 1,4-BG, and optionally additionally THF, in a hydrolysis reaction of 1,4-DAB.
It is another object of the present invention to provide a method and system for producing 1,4-BG, and optionally additionally THF, in a hydrolysis reaction where the operating or energy costs and/or capital costs associated with the system are reduced in comparison to the prior art systems.
It is another object of the present invention to provide a method and system for producing 1,4-BG, and optionally additionally THF, that promotes more efficient usage of H2O.
The inventors have discovered that the hydrolysis reaction may be shifted to favor the production of 1,4-BG with a significant reduction in the amount of H2O required to carry out the hydrolysis reactions. More specifically, the present invention provides a method and system for producing 1,4-BG in a hydrolysis reaction wherein 1,4-HAB is utilized as a starting material or reactant. The inventors have discovered that utilizing 1,4-HAB as a reactant in the hydrolysis reaction "shifts" the equilibrium of the reactions to favor the formation of 1,4-BG. The equilibrium of the hydrolysis reaction may be shifted according to the present invention by providing 1,4-HAB to the reactor in a feed stream, or by recycling at least a portion of 1,4-HAB that is produced by the hydrolysis reaction back to the reactor, or by using a combination of both. The method and system of the present invention promotes a number of significant advantages. For example, utilizing 1,4-HAB as a reactant in the hydrolysis reaction to shift the equilibrium of the reaction significantly reduces the amount of H2O required to carry out the hydrolysis reaction. Furthermore, this significant reduction in the usage of H2O can be realized with system configuration comprised of less number of reactor/separators.
Accordingly, in one aspect, the present invention provides for a method of producing 1,4-BG in a hydrolysis reaction, comprising the steps of: supplying at least one feed stream including 1,4-DAB, 1,4-HAB and H2O to at least one reactor. 1,4-DAB, 1,4-HAB and H2O are reacted in the reactor to produce at least one effluent stream that includes 1,4-BG, 1,4-HAB, H2O, unreacted 1,4-DAB and AcOH. The effluent stream is supplied to a separation system having one or more separators where preferably at least a portion of the 1,4-HAB is removed from the effluent stream and recycled back to the reactor. Alternatively, 1,4-HAB may be supplied directly to the reactor as a feed stream, as opposed to being recycled from the process itself. In yet another embodiment, 1,4-HAB is supplied using a combination of recycling a portion and providing a portion in the feed stream. However, it is preferred to recycle at least a portion of the 1,4-HAB since it is a by-product of the reaction, and thus is readily available.
Of particular advantage, the system and method of the present invention is carried out such that the following equations are satisfied. Specifically, the inventors have developed upper (Max) and lower (Min) operating bounds which factor in the capital costs and energy use of the system, and then an operating condition (Var) is selected between such bounds as shown in the following equations:
Min'=(3.79D-1.46)/n (5)
and where A is the feed rate of 1,4-DAB to the reaction system in kg/hr;
B is the feed rate of fresh 1,4-HAB to the reaction system plus the total amount of 1,4-HAB recycled to the reaction system in kg/hr;
C is the amount of 1,4-BG produced by the reaction system, and
n is the number of reactors within the reaction system.
In another aspect, the present invention provides a method of reducing the operating costs of a hydrolysis reaction to produce products including 1,4-BG wherein the cost of operating the hydrolysis reaction is defined in part by energy costs and capital costs. By using 1,4-HAB as a reactant, the equilibrium of the hydrolysis reaction is shifted toward increased production yield of 1,4-BG and decreased usage of H2O as compared to that in the absence of 1,4-HAB as a reactant. In this reaction, the energy costs are driven primarily by the H2O usage, and thus a reduction in the usage of H2O reduces the energy costs. Of further advantage, the reduction in the amount of H2O consumed in the hydrolysis reaction can provide a reduction in the capital costs of the system as the size of the reactors may be reduced.
In yet another aspect of the present invention, a hydrolysis system for producing products including 1,4-BG in a hydrolysis reaction is provided, comprising a reactor that receives reactants 1,4-DAB, H2O, 1,4-HAB and reacts said reactants to produce an effluent stream including 1,4-BG, 1,4-HAB, H2O, unreacted 1,4-DAB, and AcOH. A separation system receives the effluent stream and separates at least a portion of the 1,4-HAB from the effluent. Preferably a recycle stream is coupled to the separation system and conveys at least a portion of the 1,4-HAB back to the reactor as a reactant.
Additional objects and features of the invention will become more clearly apparent from the following detailed description and appended claims when taken in conjunction with the drawings, in which:
The present invention provides a method and system for producing 1,4-BG, and optionally additionally THF. The inventors have discovered a method and system that significantly reduces the energy or operating costs and/or capital expenditures associated with producing 1,4-BG, and optionally additionally THF. Specifically, the invention provides a system and method for producing 1,4-BG, and optionally additionally THF, wherein 1,4-HAB is provided as a feed starting material or reactant to the system. The addition of 1,4-HAB as a reactant causes a shift in the equilibrium of the hydrolysis reaction (described in detail below) such that the usage of H2O is reduced. Reducing the usage or mass flow rate of H2O reduces the energy costs of the system. As will be described in detail below, this method also reduces capital costs by providing a system configuration which may employ a combination of fewer reactors/separators and/or smaller sized equipment and still achieve a desirable yield of 1,4-BG, which compared to a prior art configuration would require multiple reactors to achieve a similar yield of 1,4-BG.
Of particular advantage, the system and method of the present invention is carried out such that the following equations are satisfied. Specifically, the inventors have developed upper (Max) and lower (Min) operating bounds which factor in the capital costs and energy use of the system, and then an operating condition (Var) is selected between such bounds as shown in the following equations:
and where A is the feed rate of 1,4-DAB to the reaction system in kg/hr;
B is the feed rate of fresh 1,4-HAB to the reaction system plus the total amount of 1,4-HAB recycled to the reaction system in kg/hr;
C is the amount of 1,4-BG produced by the reaction system, and
n is the number of reactors within the reaction system.
The advantages of this criteria can be better appreciated with consideration of "the water efficiency" of the reaction system. Consider the one reactor system of the prior art, the performance of which is shown in
Of further advantage, the above equations also account for the capital costs of the system. Specifically, when the operating condition (Var) is greater than the upper bound (Max), the reactor system design is using more capital than desired; i.e. the system is recycling too much 1,4-HAB into the reactor system. In doing so, of course we can achieve a very high energy efficiency but the penalty on the capital cost and the operating cost for separating 1,4-HAB is to large. Therefore, the system should lower its water efficiency in consideration of the overall system economics. Thus, the equations of the present invention provide for the selection of an optimized operating range between the upper and lower bounds.
Of particular advantage, providing 1,4-HAB as a reactant or starting material, either as a fresh feed stream, via a recycle stream, or by a combination of both, wherein the above equations are satisfied, improves the reaction system as indicated by a reduction in the amount of H2O consumed in comparison to same number of reactors/separators in a reaction system that does not employ 1,4-HAB as a starting material. Consequently, due to the reduction of H2O achieved by the invention, and the associated reduction in the total volumetric flowrate of the reactor system, we also reduce the size of the reaction system, which lowers the capital cost requirement of the reaction system. Additionally, the present invention employing 1,4-HAB as a starting material or reactant provides the opportunity for capital-energy cost tradeoff considerations, which allows one to tailor the system for the best overall total cost. Thus, it is possible to reduce the number of reactors, together with the H2O separator, with the expense of a slight increase in H2O consumption and hence a slight increase in energy cost and equipment size; however, there will be a reduction in the number of equipment units. In any event, the present invention provides a significant reduction in the total cost of the reaction system as compared to the prior art configurations.
This is illustrated in
A portion of the hydrolysis reactions to produce 1,4-BG and THF are shown in Table 1 below. The main reaction I is a two step reaction where in the first step I-1, 1,4-DAB is reacted with H2O to produce 1,4-HAB with a by-product of AcOH. In the second step I-2, the 1,4-HAB further reacts with the H2O to produce 1,4-BG and AcOH. Many secondary side reactions also occur (not shown). THF can be formed by using either 1,4-HAB or 1,4-BG as reactants as shown in reactions II-1 to II-4:
TABLE 1 | ||
I-1: | 1,4-DAB + H2O <==> 1,4-HAB + AcOH k1 = 0.66 | |
I-2: | 1,4-HAB + H2O <==> 1,4-BG + AcOH k2 = 0.16 | |
II-1: | 1,2-DAB + H2O <==> 1,2-HAB + AcOH | |
II-2: | 1,2-HAB + H2O <==> 1,2-BG + AcOH | |
II-3: | 1,4-HAB <==> THF + AcOH | |
II-4: | 1,4-BG <==> THF + H2O | |
The main reaction I is a reversible reaction and typically will be run at or near equilibrium condition. The inventors have determined that the equilibrium constant (k1) for the first step I-1 is much larger than the equilibrium constant (k2) for the second step I-2, in fact it is roughly four times larger. Thus, a much greater amount of H2O is necessary to form 1,4-BG from 1,4-HAB, than to form 1,4-HAB from 1,4-DAB. Accordingly, the present invention acts to shift the equilibrium of the main reaction such that the amount of 1,4-HAB available to form 1,4-BG is increased which in turn decreases the amount of H2O needed to carry out the reaction. Consequently, if the desirable product has a high 1,4-BG to 1,4-HAB ratio (1,4-BG/1,4-HAB), then the amount of H2O consumed will be very high. To reduce the total amount of H2O consumed, we can shift the product equilibrium by lowering the 1,4-BG/1,4-HAB ratio at the outlet of the final separator, i.e. the product mix, thereby utilizing more 1,4-HAB in the reaction but still increasing the total amount of product yield since the net amount of 1,4-BG formed is kept the same.
Shifting the equilibrium is accomplished according to the present invention by employing 1,4-HAB as a feed reactant or starting material to the system and by maintaining an operating condition (Var) between the upper (Max) and lower (Min) bounds. The inventors have found that when satisfying the equations 1 through 7 above, a certain composition ratio of 1,4-HAB to 1,4-BG at the outlet of the final reactor within the system will be maintained. This composition is such that the ratio of 1,4-HAB/1,4-BG in weight percent at the outlet of the final reactor in the system is in the broad range, independent of the number of reactors n, of approximately 0.4 to 2.0, more preferably in the range of approximately 0.6 to 1.5. 1,4-HAB may be supplied as a fresh reactant to the system; however, since 1,4-HAB is produced from the reaction of 1,4-DAB and H2O, it is preferred that at least a portion of the 1,4-HAB be supplied from the products of and H2O, it is preferred that at least a portion of the 1,4-HAB be supplied from the products of the reaction itself via a recycle stream, and optionally, a combination of both fresh and recycled HAB may be supplied to the reactor.
The method and system of the present invention are described in greater detail with reference to
To carry out the method of the present invention, reactants 1,4-DAB, 1,4-HAB and H2O are supplied to the reactor 42. The reactants undergo hydrolysis and produce a reaction effluent stream 49 at the outlet of the only, and in this case final, reactor 42. The effluent stream 49 includes 1,4-BG, 1,4-HAB, unreacted 1,4-DAB, AcOH and H2O. The effluent stream is conveyed to the first distillation tower 46 wherein H2O and AcOH are separated from the effluent stream and purged from the top or upper portion of the tower 46 via purge stream 51, and then conveyed typically to an acetic acid recovery (purification) section, and then sent to a wastewater treatment plant (not shown). The bottom product 53 from the first distillation tower 46 is conveyed to the second distillation tower 48 wherein at least a portion of the 1,4-HAB is separated from the final bottom product 55 and recycled back to the reactor 42 via recycle stream 45 from the top or upper portion of the tower 48. The final product is removed from the bottom of the tower 48 in product stream 55. The product stream 55 is comprised primarily of 1,4-BG, and also includes some 1,4-HAB,a small amount of unreacted 1,4-DAB and some heavy boilers. The total amount of H2O consumed in this example is about 26050 kg/hr.
In great contrast,
In comparison of the system configurations in
While the method and system of the present invention as illustrated in
From
A=12,800 kg/hr--the feed rate of 1,4-DAB,
B=0 kg/hr--the feed rate of 1,4-HAB
+4000 kg/hr--the amount of 1,4-HAB recycled to the reactor(s),
=4000 kg/hr
C=5434 kg/hr--the amount of 1,4-BG produced,
n=1--the number of reactors.
Given the above values, D is calculated according to equation 7, to give 0.814. Given the value of D, Max, Min and Min' are calculated from equations 3 to 5 to give: Max=5.47 and Min=1.11 and Min'=1.65. Then Var is calculated from equation 6 to give 0.313. Finally, the condition of equations 1 and 2; namely Min≦Var≦Max, and preferably Min'<Var<Max are considered. As we can see, in this example that Var is below the Min value, and thus this reaction system is not optimized. The amount of 1,4-HAB should preferably be increased to at least the value of the Min, which in this example is an increase in the 1,4-HAB recycle amount of about 5.3 times, or to at least approximately 22,000 kg/hr.
The method and system of the present invention may employ one or more reactors. Such an alternative embodiment is shown in
H2O is supplied to each of the reactors. The H2O may be supplied as fresh H2O as shown in
Referring again to
Accordingly, referring again to
In general, 1,4-DAB is used as a starting material and may be obtained from reacting butadiene with AcOH and oxygen and then hydrogenated to form 1,4-DAB. The hydrolysis reaction may be carried out under a variety of conditions which are conventional and well known in the art for hydrolysis reactions. It is preferred to employ a catalyst for the hydrolysis reaction, such as a ion exchange resin. An ion exchange resin such as that described in Japanese patent no. JPA52-19610 is particularly useful as a catalyst. The amount of catalyst suitably employed in the present invention is not particularly limited and need be only that minimum amount necessary to provide the basis for at least that amount which exhibits desirable catalytic activity and selectivity at the selected reaction temperature and pressure. Preferably, the reactors are fixed bed reactors packed with the cation exchange resin, and the reactants are permitted to flow through the fixed bed reactor; however, the hydrolysis reaction is not limited to this example, and other reaction methods and equipment may be used. In one exemplary illustration, the hydrolysis reaction is usually carried out at a temperature in the range of approximately 40 to 100 degrees C, and preferably at approximately 50 degrees C. Of course it should be understood that the disclosed temperature ranges are examples only, and that the temperature of the process may vary depending upon the type of reactor employed, the type of catalyst used as well as other known factors. The pressure for the hydrolysis reaction is not particularly limited and is usually selected within a range of approximately atmospheric pressure to 1 MPa.
Of particular advantage, the present invention provides 1,4-HAB as a starting material or reactant. As discussed above, very large amounts of H2O are supplied to the reactor(s), i.e. in great stoichiometric excess. Of significant advantage, the method and system of the present invention serves to reduce the amount of H2O necessary to carry out the hydrolysis reaction. Suitable concentrations of the starting materials or reactants according to the method and system of the present invention are generally supplied to the reactor such that the weight percent ratio of 1,4-HAB to 1,4-BG at the outlet of the final reactor is in the recited range of 0.4 to 2.0, and the conditions of equations 1 through 7 are met. In
When employing a recycle stream to supply at least a portion, or optionally all, of the 1,4-HAB to the reactor, the composition of the recycle stream is generally comprised of both 1,4-HAB and unreacted 1,4-DAB. The concentration of components in the recycle streams will vary, and are dependent upon the system configuration and operating conditions. In one exemplary illustration, the recycle stream is comprised of approximately, in weight percent, 85 % 1,4-HAB, 14% 1,4-BG and 1% 1,4-DAB. The ratio of 1,4-HAB to 1,4-BG in the recycle stream is in the range of approximately 5:1 to 7:1. Referring again to
A number of experiments were performed to illustrate the advantages and features of the present invention. These experiments are offered for illustration purposes only and are not intended to limit the invention in any way.
Pilot tests were run employing the system and method of the present invention. Experimental apparatus as shown in
TABLE 2 | |||
Inlet | |||
Composition | Outlet Composition | ||
Component | (wt %.) | simulated (wt %) | actual (wt %) |
H2O | 31.18 | 25.83 | 26.41 |
Acetic Acid | 0.92 | 17.89 | 18.34 |
THF | 0.00 | 0.03 | 0.11 |
1,4-DAB | 37.11 | 12.24 | 11.52 |
1,4-HAB | 26.77 | 29.15 | 28.08 |
1,4-BG | 4.01 | 14.85 | 15.54 |
Reaction time (hrs) | -- | 2.9 | 3.0 |
Reaction constant k1 | -- | 0.652 | 0.670 |
Reaction constant k2 | -- | 0.155 | 0.169 |
k1/k2 | -- | 4.21 | 3.96 |
As shown in Table 2, the simulated and actual results are comparable. Additional experiments were conducted as above, and actual results were obtained as shown in Tables 3-6 below:
TABLE 3 | |||
Inlet | |||
Composition | Outlet Composition | ||
Component | (wt %.) | simulated (wt %) | actual (wt %) |
THF | 0.003 | -- | 0.031 |
AcOH | 14.470 | -- | 31.514 |
12DAB | 4.333 | -- | 1.205 |
12HAB | 2.092 | -- | 2.267 |
12BG | 0.632 | -- | 1.867 |
14DAB | 44.037 | -- | 14.918 |
14HAB | 6.096 | -- | 18.417 |
14BG | 0.906 | -- | 4.627 |
H2O | 27.431 | -- | 25.155 |
Reaction time (hrs) | -- | 3.96 | |
Reaction constant k1 | -- | 0.652 | 0.612 |
Reaction constant k2 | -- | 0.155 | 0.138 |
k1/k2 | -- | 4.02 | 4.43 |
TABLE 4 | |||
Inlet | |||
Composition | Outlet Composition | ||
Component | (wt %.) | Simulated (wt %) | actual (wt %) |
THF | 0.000 | -- | 0.085 |
AcOH | 0.403 | -- | 14.653 |
12DAB | 1.743 | -- | 0.331 |
12HAB | 0.886 | -- | 1.650 |
12BG | 3.771 | -- | 3.888 |
14DAB | 18.443 | -- | 6.773 |
14HAB | 34.961 | -- | 24.561 |
14BG | 8.670 | -- | 19.705 |
H2O | 31.122 | -- | 28.354 |
Reaction time(hrs) | -- | 4.12 | |
Reaction constant k1 | 0.652 | 0.741 | |
Reaction constant k2 | 0.155 | 0.182 | |
k1/k2 | 4.02 | 4.07 | |
TABLE 5 | |||
Inlet | |||
Composition | Outlet Composition | ||
Component | (wt %.) | simulated (wt %) | actual (wt %) |
THF | 0.004 | -- | 0.041 |
AcOH | 15.497 | -- | 32.187 |
12DAB | 4.897 | -- | 1.613 |
12HAB | 2.426 | -- | 3.224 |
12BG | 1.513 | -- | 2.344 |
14DAB | 47.672 | -- | 17.598 |
14HAB | 3.757 | -- | 18.189 |
14BG | 0.231 | -- | 4.147 |
H2O | 24.004 | -- | 20.659 |
Reaction time(hrs) | -- | 3.98 | |
Reaction constant k1 | 0.652 | 0.637 | |
Reaction constant k2 | 0.155 | 0.156 | |
k1/k2 | 4.07 | 4.08 | |
TABLE 6 | |||
Inlet | |||
Composition | Outlet Composition | ||
Component | (wt %.) | simulated (wt %) | actual (wt %) |
THF | 0.005 | -- | 0.075 |
AcOH | 0.768 | -- | 15.598 |
12DAB | 2.077 | -- | 0.418 |
12HAB | 0.776 | -- | 2.096 |
12BG | 5.286 | -- | 4.780 |
14DAB | 22.726 | -- | 6.610 |
14HAB | 28.455 | -- | 23.079 |
14BG | 6.782 | -- | 18.038 |
H2O | 33.126 | -- | 29.306 |
Reaction time(hrs) | -- | 4.00 | |
Reaction constant k1 | 0.652 | 0.735 | |
Reaction constant k2 | 0.155 | 0.183 | |
k1/k2 | 4.07 | 4.07 | |
Tables 3 to 6 show good correlation between the reaction constants for the actual and simulated results.
Additional experiments were conducted using the one reactor stage system configuration as shown in
Further experiments were conducted using the three reactor stage system configuration shown in
As taught by the foregoing description and examples, a greatly advanced method of producing 1,4-BG is provided by the method and system of the present invention. The foregoing description of specific embodiments and examples of the invention have been presented for the purpose of illustration and description, and although the invention has been illustrated by certain of the preceding examples, it is not to be construed as being limited thereby. They are not intended to be exhaustive or to limit the invention to the precise forms disclosed, and obviously many modifications, embodiments, and variations are possible in light of the above teaching. It is intended that the scope of the invention encompass the generic area as herein disclosed, and by the claims appended hereto and their equivalents.
Iwasaka, Hiroshi, O'Young, Lionel, Ookubo, Kazuyuki, Toratani, Nobuo
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